Processes for the isomerization of paraffins of 5 and 6 carbon atoms with methylcyclopentane recovery

ABSTRACT

In an isomerization process where the isomerization effluent ( 108 ) is fractionated in a deisohexanizer ( 116 ) to provide an overhead ( 118 ) containing dimethylbutanes and a higher boiling fraction ( 122 ) containing normal hexane, the higher boiling is contacted with a selectively permeable membrane ( 124 ) to provide a retentate containing methylcyclopentane ( 128 ). If desired, the normal hexane-containing permeate can be recycled for isomerization. The preferred membranes are sieving membranes having a C 6  Permeate Flow Index of at least 0.01 and a C 6  Permeate Flow Ratio of at least 1.25:1.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Division of application Ser. No. 11/851,565 filedSep. 7, 2007, now U.S. Pat. No. 7,638,674, the contents of which arehereby incorporated by reference in its entirety.

BACKGROUND OF THE INVENTION

This invention relates to improved processes for the isomerization ofparaffins of 5 and 6 carbon atoms, e.g., to provide isomerate havingenhanced Research Octane Number (RON) for blending into gasoline pools,and particularly to such processes using a deisohexanizer.

Processes for the isomerization of paraffins into more highly branchedparaffins are widely practiced. Particularly important commercialisomerization processes are used to increase the branching, and thus theoctane value of refinery streams containing paraffins of 4 to 8,especially 5 and 6, carbon atoms. The isomerate is typically blendedwith a refinery reformer effluent to provide a blended gasoline mixturehaving a desired research octane number (RON).

The isomerization process proceeds toward a thermodynamic equilibrium.Hence, the isomerate will still contain normal paraffins that have lowoctane ratings and thus detract from the octane rating of the isomerate.Provided that adequate high octane blending streams such as alkylate andreformer effluent is available and that gasolines of lower octaneratings, such as 85 and 87 RON, are in demand, the presence of thesenormal paraffins in the isomerate has been tolerated.

Where circumstances demand higher RON isomerates, the isomerizationprocesses have been modified by separating the normal paraffins from theisomerate and recycling them to the isomerization reactor. Thus, notonly are normal paraffins that detract from the octane rating removedfrom the isomerate but also their return to the isomerization reactorincreases the portion of the feed converted to the more highly desiredbranched paraffins.

The major processes for the separation of the normal paraffins from theisomerate are the use of adsorptive separation such as disclosed in U.S.Pat. Nos. 4,717,784 and 4,804,802, and distillation. The most frequentlypracticed isomerization processes that recycle normal paraffins use adeisohexanizer. A deisohexanizer is one or more distillation columnswhere an overhead containing branched C₆ paraffins such asdimethylbutanes (2,2-dimethylbuthane and 2,3-dimethylbutane) and lightercomponents is obtained as the isomerate product for, e.g., blending forgasolines, and a side-stream containing normal hexane and similarlyboiling components such as methylpentanes (2-methylpentane and3-methylpentane) and methylcyclopentane is recycled to the isomerizationreactor. The problem with a deisohexanizer is that the lower boilingproduct stream contains n-pentane which has a low RON value.

The use of adsorptive separation instead of a deisohexanizer enablesn-pentane to be removed, thereby providing a high RON motor fuel, oftenin the range of 91 to 93.

Separation of linear from branched paraffins has also been proposed, butmembranes have yet to find a practical, commercial application. U.S.Pat. No. 5,069,794 discloses microporous membranes containingcrystalline molecular sieve material. At column 8, lines 11 et seq.,potential applications of the membranes are disclosed including theseparation of linear and branched paraffins. See also, U.S. Pat. No.6,090,289, disclosing a layered composite containing molecular sievethat could be used as a membrane. Among the potential separations inwhich the membrane may be used that are disclosed commencing at column13, line 6, include the separation of normal paraffins from branchedparaffins. U.S. Pat. Nos. 6,156,950 and 6,338,791 discuss permeationseparation techniques that may have application for the separation ofnormal paraffins from branched paraffins and describe certain separationschemes in connection with isomerization. US 2003/0196931 discloses atwo-stage isomerization process for up-grading hydrocarbon feeds of 4 to12 carbon atoms.

Recently, Bourney, et al., in WO 2005/049766 disclose a process forproducing high octane gasoline using a membrane to remove, inter alia,n-pentane from an isomerized stream derived from the overhead of adeisohexanizer. A side cut from the deisohexanizer is as a sweep fluidon the permeate side of the membrane. The mixture of the permeate andsweep fluid is recycled to the isomerization reactor. In a computersimulation based upon the use of an MFI on alumina membrane, example 1of the publication indicates that 5000 square meters of membrane surfacearea is required to remove 95 mass percent of n-pentane from theoverhead from a deisohexanizer distillation column. At the flow rate offeed to the permeator (75000 kg/hr. having 20.6 mass percent n-pentane),the flux of n-pentane used in the simulation appears to be in the orderof 0.01 gram moles/m²·s at 300° C. The RON of the product with then-pentane removed is said to be 91.0.

The use by Bourney, et al., of a side cut from the deisohexanizer as asweep fluid for the membrane separation results in recycling valuablehigh octane compounds such as methylpentanes and methylcyclopentane backto the isomerization reactor. In Table 1, Bourney, et al., state thatthe concentration of methylcyclopentane is 9.7 mass percent. Nomethylcyclopentane is in the product stream. Additionally, the sweepstream contains 4.5 mass percent 2,3-dimethylbutane which is alsorecycled to the isomerization reactor. As the isomerization reactionwill distribute the isomers toward equilibrium, they sacrifice per passyield of high RON fuel for RON.

The use of zeolite membranes is suggested as a suitable technique forseparating linear molecules. See, for instance, paragraphs 0008 and0032. U.S. Pat. No. 6,818,333 discloses thin zeolite membranes that aresaid to have a permeability of n-butane of at least 6·10⁻⁷ mol/m²·s·Paand a selectivity of at least 250 of n-butane to isobutane.

Changes in environmental and fuel efficiency regulations can have aprofound effect on the demand for isomerate of higher octane-ratings.For instance, requirements to reduce benzene content of gasolines wouldnecessitate increasing the octane rating of isomerate and “once-through”isomerization processes will be required to be retrofitted to a processthat separates and recycles normal paraffins to the isomerizationreactor. Even existing processes that use deisohexanizers may berequired to provide isomerate of enhanced octane rating.

Accordingly, economically viable, and simple to operate processes toenhance the octane rating of deisohexanizer overhead are sought.

For the purposes of the following discussion of the invention, thefollowing membrane properties are defined.

Microporous

Microporous and microporosity refer to pores having effective diametersof between 0.3 to 2 nanometers.

Mesoporous

Mesoporous and mesoporosity refer to pores having effective diameters ofbetween 2 and 50 nanometers.

Macroporous

Macroporous and macroporosity refer to pores having effective diametersof greater than 50 nanometers.

Nanoparticle

Nanoparticles are particles having a major dimension up to 100nanometers.

Molecular Sieves

Molecular sieves are materials having microporosity and may beamorphous, partially amorphous or crystalline and may be zeolitic,polymeric, metal, ceramic or carbon.

Sieving Membrane

Sieving membrane is a composite membrane containing a continuous ordiscontinuous selective separation medium containing molecular sievebarrier. A barrier is the structure that exists to selectively blockfluid flow in the membrane. In a continuous sieving membrane, themolecular sieve itself forms a continuous layer that is sought to bedefect-free. The continuous barrier may contain other materials such aswould be the case with mixed matrix membranes. A discontinuous sievingmembrane is a discontinuous assembly of molecular sieve barrier in whichspaces, or voids, exist between particles or regions of molecular sieve.These spaces or voids may contain or be filled with other solidmaterial. The particles or regions of molecular sieve are the barrier.The separation effected by sieving membranes may be on steric propertiesof the components to be separated. Other factors may also affectpermeation. One is the sorptivity or lack thereof by a component and thematerial of the molecular sieve. Another is the interaction ofcomponents to be separated in the microporous structure of the molecularsieve. For instance, for some zeolitic molecular sieves, the presence ofa molecule, say, n-hexane, in a pore, may hinder 2-methylpentane fromentering that pore more than another n-hexane molecule. Hence, zeolitesthat would not appear to offer much selectivity for the separation ofnormal and branched paraffins solely from the standpoint of molecularsize, may in practice provide greater selectivities of separation.

C₆ Permeate Flow Index

The permeability of a sieve membrane, i.e., the rate that a givencomponent passes through a given thickness of the membrane, often varieswith changes in conditions such as temperature and pressure, absoluteand differential. Thus, for instance, a different permeation rate may bedetermined where the absolute pressure on the permeate side is 1000 kParather than that where that pressure is 5000 kPa, all other parameters,including pressure differential, being constant. Accordingly, a C₆Permeate Flow Index is used herein for describing sieving membranes. TheC₆ Permeate Flow Index for a given membrane is determined by measuringthe rate (gram moles per second) at which a substantially pure normalhexane (preferably at least 95 mass-percent normal hexane) permeates themembrane at approximately 150° C. at a retentate side pressure of 1000kPa absolute and a permeate-side pressure of 100 kPa absolute. The C₆Permeate Flow Index reflects the permeation rate per square meter ofretentate-side surface area but is not normalized to membrane thickness.Hence, the C₆ Permeate Flow Index for a given membrane will be in theunits of gram moles of normal hexane permeating per second per squaremeter of retentate-side membrane surface area.

C₆ Permeate Flow Ratio

The C₆ Permeate Flow Ratio for a given sieve membrane is the ratio ofthe C₆ Permeate Flow Index (n-hexane) to an i-C₆ Permeate Flow Indexwherein the i-C₆ Permeate Flow Index is determined in the same manner asthe C₆ Permeate Flow Index but using substantially pure dimethylbutanes(regardless of distribution between 2,2-dimethylbutane and2,3-dimethylbutane) (preferably at least 95 mass-percentdimethylbutanes).

SUMMARY OF THE INVENTION

By this invention improvements are made to isomerization processes forupgrading the octane rating of paraffin feedstocks comprising 5 and 6carbon atoms where the processes use deisohexanizers to provide a lowerboiling dimethylbutanes-containing fraction and a higher boiling normalhexane-containing fraction. In accordance with this invention, membranesare used to recover from the higher boiling normal hexane-containingfraction components of higher octane rating such as methylcyclopentaneand dimethylbutanes. These higher octane rating components can be usedfor blending with motor fuels. As only a portion of the isomerizationeffluent is subjected to membrane treatment, the surface area ofmembrane required can be reduced, thereby enhancing economic viabilityof using membranes.

Preferably, at least a portion of the normal hexane-containing permeatefrom the membrane separation is recycled for isomerization. As theconcentration of normal hexane in the permeate is higher than that inthe higher boiling fraction, the volume of recycle is reduced ascompared to recycling the same amount of normal hexane but without thebenefit of the membrane separation. The ability of the processes of theinvention to reduce the volume of recycle to the isomerization reactorcan provide several advantages. For instance, the reduced volume ofrecycle allows for an increase in feed to the isomerization reactor fora given conversion, thus increasing the capacity of the isomerizationreactor. Also, by reducing the amount of higher-octane components suchas methylcyclopentane and dimethylbutanes that would otherwise berecycled to the isomerization reactor, the equilibrium nature of theisomerization reactions will enable more higher-octane product to beproduced per unit of feedstock.

The broad aspects of the processes of this invention comprise:

-   a. isomerizing a feedstock comprising paraffins having 5 and 6    carbon atoms wherein at least 15 mass-percent of the feedstock is    linear paraffin under isomerization conditions including the    presence of isomerization catalyst to provide an isomerization    effluent containing linear paraffins but in a concentration less    than that in the feedstock,-   b. distilling at least a portion, preferably at least 90    mass-percent and most preferably essentially all, of the    isomerization effluent to provide a lower boiling fraction    containing dimethylbutanes and lighter paraffins and a normal    hexane-containing fraction containing normal hexane, methylpentanes,    dimethylbutanes and methylcyclopentane,-   c. contacting at least a portion, preferably at least 90    mass-percent and most preferably essentially all, of the normal    hexane-containing fraction from step b with a retentate-side of a    selectively permeable membrane under conditions including sufficient    membrane surface area and pressure differential across the membrane    to provide a retentate fraction that has an increased concentration    of methylcyclopentane and dimethylbutanes, and to provide across the    membrane at a permeate-side, a permeate fraction having an increased    concentration of normal hexane and methylpentanes, said permeate    fraction containing at least 75, preferably at least 90,    mass-percent of the normal hexane contained in the normal    hexane-containing fraction contacted with the membrane, and-   d. withdrawing from step c the retentate fraction.

Preferably at least a portion, more preferably at least 90 mass percent,and most preferably essentially all, of the permeate fraction of step cis recycled to step a.

Preferably at least 25, more preferably at least 30, mass-percent of themethylpentanes contained in the normal hexane-containing streamcontacting the membrane is contained in the permeate fraction. In manyinstances, the concentration of normal hexane to the total permeate willbe less than 90 mass-percent, e.g., from 25 to 90, say, 40 to 80,mass-percent. In some aspects of the processes of the invention, thewithdrawn retentate fraction is greater than 10, say, 15 to 50,mass-percent of the normal hexane-containing fraction contacting themembrane. Thus, the volume of the recycle to the isomerization of step ais less than in an identical process except that the normalhexane-containing fraction is not subjected to the membrane separation.

The retentate fraction of step d contains significant amounts ofmethylcyclopentane and thus has an attractive octane rating. Often atleast 50, preferably at least 80, mass-percent of the methylcyclopentanein the normal hexane-containing fraction contacting the membrane isretained in the retentate fraction.

The separation of monomethylpentanes from dimethylbutanes is difficultdue to the proximity of boiling points and thus not only does adeisohexanizer use an extensive number of distillation trays, often inthe range of 80 trays, but also a large reflux to feed ratio, e.g., 2:1to 3:1. Hence, the operation of the deisohexanizer requires substantialreboiler heat. By the use of the processes of this invention, asignificant portion of the dimethylbutanes contained in the normalhexane-containing fraction remain in the retentate fraction and thusrecovered with the methylcyclopentane for use in the motor fuel pool.Preferably the distillation of step b is operated such that the normalhexane-containing fraction contains dimethylbutanes, say, at least 2,and sometimes from 5 to 30, mass-percent of the dimethylbutanescontained in the isomerization effluent from step a. Preferably at least30, more preferably at least 70, mass-percent of the dimethylbutanescontained in the normal hexane-containing fraction, is retained in theretentate fraction. Thus, the withdrawn retentate can be used as motorfuel or added to a pool to provide a motor fuel. Accordingly, for anexisting deisohexanizer, the reflux ratio can be reduced, sometimes by10 to 50 percent, resulting in energy savings without undue loss in theoctane rating of the product.

Preferably the membrane is a sieving membrane having a C₆ Permeate FlowIndex of at least 0.01, more preferably at least 0.02, and a C₆ PermeateFlow Ratio of at least 1.25:1, more preferably at least 1.3:1, and often1.35:1 to 5:1 or 6:1.

The invention also pertains to apparatus suitable for conducting theprocesses of this invention. In its broader aspects, the apparatus ofthis invention is an apparatus for isomerization of a feedstockcomprising paraffins having between 5 and 6 carbon atoms to provide agasoline fraction comprising:

a. an isomerization reactor (106) being adapted to receive feedstock atan inlet and having an outlet,

b. a deisohexanizer (116) having an inlet in fluid communication withthe outlet of isomerization reactor (106), a lower boiling outletadapted to remove a lower boiling fraction via line (118), a outlet toprovide a side-cut fraction and a higher boiling outlet; and

c. a membrane separator (124) having a feed side inlet in fluidcommunication with the outlet to provide a side-cut fraction of thedeisohexanizer (116), a feed side outlet in fluid communication withline (118) from the lower boiling outlet of the deisohexanizer (116),and a permeate outlet in fluid communication with the inlet of theisomerization reactor (106).

DESCRIPTION OF THE FIGURE

The FIGURE is a schematic representation of processes in accordance withthis invention using a stabilizer column prior to a deisohexanizer.

DETAILED DESCRIPTION OF THE INVENTION

Isomerization

Any suitable paraffin-containing feedstock may be used in the processesof this invention. Naphtha feedstocks are the most often used as thefeedstocks to isomerization processes. Naphtha feedstocks compriseparaffins, naphthenes, and aromatics, and may comprise small amounts ofolefins, boiling within the gasoline range. Feedstocks which may beutilized include straight-run naphthas, natural gasoline, syntheticnaphthas, thermal gasoline, catalytically cracked gasoline, partiallyreformed naphthas or raffinates from extraction of aromatics. Thefeedstock essentially is encompassed by the range of a full-rangenaphtha, or within the range of 0° to 230° C. Usually the feedstock islight naphtha having an initial boiling point of 10° to 65° C. and afinal boiling point from 75° to 110° C.; preferably, the final boilingpoint is less than 95° C.

Naphtha feedstocks generally contain small amounts of sulfur compoundsamounting to less than 10 mass parts per million (mppm) on an elementalbasis. Preferably the naphtha feedstock has been prepared from acontaminated feedstock by a conventional pretreating step such ashydrotreating, hydrorefining or hydrodesulfurization to convert suchcontaminants as sulfurous, nitrogenous and oxygenated compounds to H₂S,NH₃ and H₂O, respectively, which can be separated from hydrocarbons byfractionation. This conversion preferably will employ a catalyst knownto the art comprising an inorganic oxide support and metals selectedfrom Groups VIB(IUPAC 6) and VIII(IUPAC 9-10) of the Periodic Table.Water can act to attenuate catalyst acidity by acting as a base, andsulfur temporarily deactivates the catalyst by platinum poisoning.Feedstock hydrotreating as described hereinabove usually reduceswater-generating oxygenates and deactivating sulfur compounds tosuitable levels, and other means such as adsorption systems for theremoval of sulfur and water from hydrocarbon streams generally are notrequired. It is within the ambit of the present invention that thisoptional pretreating step be included in the present processcombination.

The principal components of the preferred feedstock are cyclic andacyclic paraffins having from 4 to 8 carbon atoms per molecule (C₄ toC₈), especially C₅ and C₆, and smaller amounts of aromatic and olefinichydrocarbons also may be present. Usually, the concentration of C₇ andheavier components is less than 20 mass-percent of the feedstock, andthe concentration of C₄ and lighter components is less than 20,preferably less than 10, mass-percent of the feedstock. The mass ratioof C₅ to C₆ components in the preferred feedstocks is 1:10 to 1:1.

Although there are no specific limits to the total content in thefeedstock of cyclic hydrocarbons, the feedstock generally containsbetween 2 and 40 mass-percent of cyclics comprising naphthenes andaromatics. The aromatics contained in the naphtha feedstock, althoughgenerally amounting to less than the alkanes and cycloalkanes, maycomprise from 2 to 20 mass-percent and more usually 5 to 10 mass-percentof the total. Benzene usually comprises the principal aromaticsconstituent of the preferred feedstock, optionally along with smalleramounts of toluene and higher-boiling aromatics within the boilingranges described above.

In general, linear paraffins constitute at least 15, often from 40,preferably at least 50, mass-percent to essentially all of thefeedstocks used in the processes of this invention. For naphthafeedstocks, linear paraffins are typically present in amounts of atleast to 50, say, 50 to 90, mass-percent. The mass ratio of non-linearparaffins to linear paraffins in the feedstocks is often less than 1:1,say, 0.1:1 to 0.95:1. Non-linear paraffins include branched acyclicparaffins and substituted or unsubstituted cycloparaffins. Othercomponents such as aromatics and olefinic compounds may also be presentin the feedstocks as described above.

The feedstock is passed to one or more isomerization zones. In theaspects of this invention where normal hexane is recycled, the feedstockand recycle are usually admixed prior to entry into the isomerizationzone, but if desired, may be separately introduced. In any case, thetotal feed to the isomerization zone is referred to herein as theisomerization feed. The recycle may be provided in one or more streams.As discussed later, the recycle contains linear paraffins. Theconcentration of linear paraffins in the isomerization feed will notonly depend upon the concentration of linear paraffins in the feedstockbut also the concentration in the recycle and the relative amount ofrecycle to feedstock, which can fall within a wide range. Often, theisomerization feed has a linear paraffins concentration of at least 30,say, between 35 and 90, preferably 40 to 70, mass-percent, and a moleratio of non-linear paraffins to linear paraffins of between 0.2:1 to1.5:1, and sometimes between 0.4:1 to 1.2:1.

In the isomerization zone the isomerization feed is subjected toisomerization conditions including the presence of isomerizationcatalyst preferably in the presence of a limited but positive amount ofhydrogen as described in U.S. Pat. Nos. 4,804,803 and 5,326,296, bothherein incorporated by reference. The isomerization of paraffins isgenerally considered a reversible first order reaction. Thus, theisomerization reaction effluent will contain a greater concentration ofnon-linear paraffins and a lesser concentration of linear paraffins thandoes the isomerization feed. In preferred embodiments of this invention,the isomerization conditions are sufficient to isomerize at least 20,preferably, between 30 and 60, mass-percent of the normal paraffins inthe isomerization feed. In general, the isomerization conditions achieveat least 70, preferably at least 75, say, 75 to 97, percent ofequilibrium for C₆ paraffins present in the isomerization feed. In manyinstances, the isomerization reaction effluent has a mass ratio ofnon-linear paraffins to linear paraffins of at least 2:1, preferablybetween 2.5 to 4:1.

The isomerization catalyst is not critical to the broad aspects of theprocesses of this invention, and any suitable isomerization catalyst mayfind application. Suitable isomerization catalysts include acidiccatalysts using chloride for maintaining the sought acidity and sulfatedcatalysts. The isomerization catalyst may be amorphous, e.g. based uponamorphous alumina, or zeolitic. A zeolitic catalyst would still normallycontain an amorphous binder. The catalyst may comprise a sulfatedzirconia and platinum as described in U.S. Pat. No. 5,036,035 andEuropean application 0 666 109 A1 or a platinum group metal on chloridedalumina as described in U.S. Pat. Nos. 5,705,730 and 6,214,764. Anothersuitable catalyst is described in U.S. Pat. No. 5,922,639. U.S. Pat. No.6,818,589 discloses a catalyst comprising a tungstated support of anoxide or hydroxide of a Group IVB (IUPAC 4) metal, preferably zirconiumoxide or hydroxide, at least a first component which is a lanthanideelement and/or yttrium component, and at least a second component beinga platinum-group metal component. These documents are incorporatedherein for their teaching as to catalyst compositions, isomerizationoperating conditions and techniques.

Contacting within the isomerization zones may be effected using thecatalyst in a fixed-bed system, a moving-bed system, a fluidized-bedsystem, or in a batch-type operation. A fixed-bed system is preferred.The reactants may be contacted with the bed of catalyst particles inupward, downward, or radial-flow fashion. The reactants may be in theliquid phase, a mixed liquid-vapor phase, or a vapor phase whencontacted with the catalyst particles, with excellent results beingobtained by application of the present invention to a primarilyliquid-phase operation. The isomerization zone may be in a singlereactor or in two or more separate reactors with suitable means toensure that the desired isomerization temperature is maintained at theentrance to each zone. Two or more reactors in sequence are preferred toenable improved isomerization through control of individual reactortemperatures and for partial catalyst replacement without a processshutdown.

Isomerization conditions in the isomerization zone include reactortemperatures usually ranging from 40° to 250° C. Lower reactiontemperatures are generally preferred in order to favor equilibriummixtures having the highest concentration of high-octane highly branchedisoalkanes and to minimize cracking of the feed to lighter hydrocarbons.Temperatures in the range of from 100° to 200° C. are preferred in thepresent invention. Reactor operating pressures generally range from 100kPa to 10 MPa absolute, preferably between 0.5 and 4 MPa absolute.Liquid hourly space velocities range from 0.2 to 25 volumes ofisomerizable hydrocarbon feed per hour per volume of catalyst, with arange of 0.5 to 15 hr⁻¹ being preferred.

Hydrogen is admixed with or remains with the isomerization feed to theisomerization zone to provide a mole ratio of hydrogen to hydrocarbonfeed of from 0.01 to 20, preferably from 0.05 to 5. The hydrogen may besupplied totally from outside the process or supplemented by hydrogenrecycled to the feed after separation from isomerization reactoreffluent. Light hydrocarbons and small amounts of inerts such asnitrogen and argon may be present in the hydrogen. Water should beremoved from hydrogen supplied from outside the process, preferably byan adsorption system as is known in the art. In a preferred embodimentthe hydrogen to hydrocarbon mol ratio in the reactor effluent is equalto or less than 0.05, generally obviating the need to recycle hydrogenfrom the reactor effluent to the feed.

Especially where a chlorided catalyst is used for isomerization, theisomerization reaction effluent is contacted with a sorbent to removeany chloride components such as disclosed in U.S. Pat. No. 5,705,730.

Distillation and Membrane Separation

The isomerization reaction effluent is subjected to one or moreseparation operations to provide a product fraction of an enhancedoctane rating and, optionally, to remove other components such ashydrogen, lower alkanes and, especially with respect to chloridedcatalysts, halogen compounds.

In a commonly practiced isomerization process, the isomerization isconducted in the liquid phase and the isomerization reaction effluent ispassed to a product separator in which a gaseous overhead containinghydrogen and lower alkane is obtained. At least a portion of thishydrogen can be recycled to the isomerization reactor for providing atleast a portion of the sought hydrogen for the isomerization. The liquidbottoms is passed to a distillation assembly (deisohexanizer) to providea lower boiling fraction containing dimethylbutanes and a higher boilingnormal hexane-containing fraction. Most often, the deisohexanizer isadapted to provide the normal hexane-containing stream as a side streamand provides a bottoms stream comprising normal heptane. Thedeisohexanizer may be a packed or frayed column and typically operateswith a top pressure of between 50 and 500 kPa (gauge) and a bottomstemperature of between 75° and 170° C.

The composition of the lower boiling fraction from the deisohexanizerwill depend upon the operation and design of the assembly and anyseparation processes to which the isomerization effluent has beensubjected. For instance, if the stream to the deisohexanizer containslights such as C₁ to C₄ compounds, the deisohexanizer may be adapted toprovide an overhead fraction containing these lights, and a side-drawfraction containing C₅ compounds and branched C₆ compounds, especiallydimethylbutanes. Typically the lower boiling fraction contains 20 to 60mass-percent dimethylbutanes; 10 to 40 mass-percent normal pentane and20 to 60 mass-percent isopentane and butane. Depending upon theoperation of the deisohexanizer, the lower boiling fraction may alsocontain significant, e.g., at least 10 mass-percent methylpentanes. Thedeisohexanizer may also be adapted to provide a C₅-rich stream inaddition to the lower boiling stream.

The higher boiling normal hexane-containing fraction also containsmethylpentanes and methylcyclopentane. As stated earlier, the processesof this invention permit the deisohexanizer to be operated moreeconomically resulting in a greater concentration of dimethylbutanes inthe normal hexane-containing fraction. Often the normalhexane-containing fraction will contain 2 to 10 mass-percentdimethylbutanes; 5 to 50 mass-percent normal hexane; 20 to 60mass-percent methylpentanes, and 5 to 25 mass-percentmethylcyclopentane. Typically, the deisohexanizer will be designed toprovide a side stream that contains methyl pentanes, methylcyclopentane,normal hexane, dimethylbutanes and cyclohexane, and a bottoms streamthat contains cyclohexane and C₇+ hydrocarbons. If the normalhexane-containing fraction were the bottom fraction of thedeisohexanizer, that fraction would also contain such heavierhydrocarbons.

As stated above, the ability to recover dimethylbutanes from the higherboiling normal hexane-containing fraction enables the distillation to beconducted with a lower reflux ratio. The reflux ratio used will dependupon the nature of the feed to the column as well as the design of thecolumn and thus can vary over a broad range, e.g., from 1.5:1 to 2.5:1on a mass basis of reflux to feed.

At least a portion, preferably at least 50, and more preferably at least80, mass-percent to substantially all of the normal hexane-containingfraction from the deisohexanizer is contacted with the retentate side ofa selective membrane to provide a retentate fraction of theisomerization reaction effluent that has a reduced concentration oftotal linear paraffins, and to provide across the membrane at apermeate-side, a permeate fraction having an increased concentration oftotal linear paraffins. The permeate fraction contains at least 75mass-percent of the normal hexane, preferably at least 75 mass-percentof the normal hexane, in the fraction contacted with the membrane. Theretentate preferably contains at least 50, more preferably at least 80to substantially all of the methylcyclopentane contained in the fractioncontacting the membrane. In preferred aspects of the invention, themembrane allows at least 25, say, 30 to 90, mass-percent of themethylpentanes contained in the normal hexane-containing fractioncontacting the membrane to permeate.

A pressure drop is maintained across the membrane in order to effect thedesired separation at suitable permeation rates. The membrane may be ofany suitable type including diffusion and sieving, and may beconstructed of inorganic, organic or composite materials. For diffusionmembranes, the driving force is the differential in partial pressuresbetween the retentate and the permeate sides. In sieving membranes, theabsolute pressure drop becomes a significant component of the drivingforce independent of partial pressures or concentrations. The preferredmembranes are sieving membranes having a C₆ Permeate Flow Index of atleast 0.01 and a C₆ Permeate Flow Ratio of at least 1.25:1. The sievingmembranes are discussed in more detail below.

In the membrane separations, the pressure drop is often in the range of0.1 to 10, preferably 0.2 to 2, MPa. In practice, the normalhexane-containing fraction will be contacted with the retentate side ofthe membranes without additional compression to minimize capital andoperating costs. The temperature for the membrane separation will dependin part on the nature of the membrane and on the temperature of thefraction. Thus, for polymer-containing membranes, temperatures should besufficiently low that the strength of the membrane is not undulyadversely affected. In most instances, the temperature for theseparation is the temperature of the deisohexanizer fraction. Often thetemperature is in the range of 25° C. to 150° C. Thus, the conditions ofthe membrane separation may provide for a liquid or gas or mixed phaseon the retentate side of the membrane. Regardless of the phase of thefluid on the retentate side, the permeate may be a gas. If the fluid onthe retentate side of the membrane is in the liquid phase, the permeatemay be liquid, gaseous or mixed phase.

Any suitable selectively permeable membrane may be used in the apparatusand processes of this invention. The preferred membranes are sievingmembranes. The membranes used in the processes of this invention arecharacterized in having high flux, i.e., having a C₆ Permeate Flow Indexof at least 0.01. The membranes may be in any suitable form such ashollow fibers, sheets, and the like which can be assembled in aseparator unit such as bundled hollow fibers or flat plate or spiralwound sheet membranes. The physical design of the membranes shouldenable, when assembled in the separator unit, sufficient pressure dropacross the membrane to provide desirable flux. For hollow fibermembranes, the high pressure side (retentate side) is usually at theoutside of the hollow fiber. The flow of the permeate may be co-current,countercurrent or cross-current with respect to the flow of the fluid onthe retentate side of the membrane.

Sufficient membrane surface area is provided that under steady stateconditions at least 75, preferably at least 80, and more preferably atleast 90, mass-percent of the normal hexane contained in the fractionfrom the deisohexanizer is contained in the permeate. The concentrationof normal hexane will depend upon the selectivity of the membrane. Whilethe membrane may be highly selective and provide a permeate containing99 mass-percent or more of normal hexane, advantageous embodiments ofthis invention can be achieved with lesser purity permeates. Theconcentration of normal hexane to the total permeate in theseembodiments will be less than 90 mass-percent, e.g., from 25 to 90, say,40 to 80, mass-percent. The remainder of the effluent will typically bemethylpentanes and some methylcyclopentane and dimethylbutanes that passthrough the membrane.

The preferred high flux, sieving membranes permit a portion of branchedparaffins to permeate. The relative rates of permeation will depend uponthe molecular configuration of the paraffins. Methyl pentanes will passmore readily through the membrane than the dimethylbutanes andcyclopentane.

Preferably at least a portion of the permeate is recycled to theisomerization step. The permeate will contain linear paraffins that willbe subjected to isomerization conditions during the isomerization step.

Sieving Membranes

The preferred sieving membranes may be of various types, for instance,molecular sieves, pore-containing ceramic, metal, polymeric or carbonmembranes, or composite membranes having a highly porous polymeric,metallic, molecular sieve, ceramic or carbon support with a thin sievinglayer or barrier (molecular sieve), e.g., zeolitic, polymeric, metal,ceramic or carbon, having microporosity.

The membranes may be continuous or discontinuous. A discontinuousmembrane comprises an assembly of small particle size microporousbarrier whereas a continuous membrane comprises a continuous layer ofmicroporous barrier. The membranes may be formed of a single material orthey may be composites containing microporous barrier and support and,optionally, other structure. When making a thin, continuous barrierlayer, as the thickness of the sieving layer decreases, the difficultiesin obtaining a defect-free layer increase. As the processes of thisinvention do not require high selectivity, the membranes can containminor defects. Typically continuous membranes are made by depositing orgrowing on a meso/macroporous structure, a continuous, thin layer ofmicroporous barrier. Discontinuous assemblies of nano-sized microporousbarrier enable very small permeating thicknesses to be achieved, butwith the potential of by-pass. Discontinuous membranes use ameso/macroporous structure with which the microporous barrier isassociated.

Examples of zeolite barrier include small pore molecular sieves such asSAPO-34, DDR, AlPO-14, AlPO-17, AlPO-18, AlPO-34, SSZ-62, SSZ-13,zeolite 3A, zeolite 4A, zeolite 5A, zeolite KFI, H-ZK-5, LTA, UZM-9,UZM-13, ERS-12, CDS-1, Phillipsite, MCM-65, and MCM-47; medium poremolecular sieves such as silicalite, SAPO-31, MFI, BEA, and MEL; largepore molecular sieves such as FAU, OFF, NaX, NaY, CaY, 13X, and zeoliteL; and mesoporous molecular sieves such as MCM-41 and SBA-15. A numberof types of molecular sieves are available in colloidal (nano-sizedparticle) form such as A, X, L, OFF, MFI, and SAPO-34. The zeolites mayor may not be metal exchanged.

Other types of sieving materials include carbon sieves; polymers such asPIMs (polymers of intrinsic microporosity) such as disclosed by McKeown,et al., Chem. Commun., 2780 (2002); McKeown, et al., Chem. Eur. J.,11:2610 (2005); Budd, et al., J. Mater. Chem., 13:2721 (2003); Budd, etal., Adv. Mater., 16:456 (2004) and Budd, et al., Chem. Commun., 230(2004); polymers in which porosity is induced by pore-forming agentssuch as poly(alkylene oxide), polyvinylpyrrolidone; cyclic organic hostssuch as cyclodextrins, calixarenes, crown ethers, and spherands;microporous metal-organic frameworks such as MOF-5 (or IRMOF-1); glass,ceramic and metal shapes into which microporosity has been introduced.

In composite membranes, a meso/macroporous structure is used. Themeso/macroporous structure serves one or more functions depending uponthe type membrane. It can be the support for the membrane composite, itcan be an integral part of forming the microporous barrier, it can bethe structure upon which or in which the microporous barrier is located.The meso/macroporous structure can be continuous or discontinuous, andthe meso/macroporosity may thus be channels through the material of themeso/macroporous structure or be formed between particles that form themeso/macroporous structure. Examples of the latter are the AccuSep™inorganic filtration membranes available from the Pall Corp. having azirconia layer on a porous metal support wherein the zirconia is in theform of spherical crystals.

The meso/macroporous structure preferably defines channels, or pores, inthe range of 2 to 500, preferably, 10 to 250, more preferably between 20and 200, nanometers in diameter, and has a high flux. In more preferredembodiments, the C₆ Permeant Flow Index of the meso/macroporousstructure is at least 1, and most preferably at least 10, and sometimesat least 1000. The meso/macroporous structure may be isotropic oranisotropic. The meso/macropores may be relatively straight or tortuous.

The meso/macroporous structure may be composed of inorganic, organic ormixed inorganic and organic material. The selection of the material willdepend upon the conditions of the separation as well as the type ofmeso/macroporous structure formed. The material of the meso/macroporousstructure may be the same or different than the material for themolecular sieve. Examples of porous structure compositions includemetal, alumina such as alpha-alumina, gamma alumina and transitionaluminas, molecular sieve, ceramics, glass, polymer, and carbon. Inpreferred embodiments, defects in the substrate are repaired prior toproviding the barrier or precursor to the barrier. In anotherembodiment, the substrate may be treated with a silica sol to partiallyocclude pores and facilitate deposition of the barrier or precursor tothe barrier. The silica particles will still provide sufficient spacebetween their interstices to allow high flux rates. Another technique isto coat the support with silicon rubber or other polymer that permitshigh flux but occludes defects in the support or in the barrier.

If the meso/macroporous structure does not so serve, the membrane cancontain a porous support for the meso/macroporous structure. The poroussupport is typically selected on the basis of strength, tolerance forthe conditions of the intended separation and porosity.

The AccuSep™ inorganic filtration membranes available from Pall Corp.and similar types of meso/macroporous structures are particularlyadvantageous since the meso/macroporous structure can be thin therebyavoiding undue thicknesses of molecular sieve being grown. Further, thezirconia is relatively inert to zeolite-forming precursor solutions andsynthesis and calcination conditions, making it a preferredmeso/macroporous structure for these types of sieving membrane.

High flux is achieved through at least one of the following techniques:first, using a larger pore than required for normal alkane to pass; andsecond, using an extremely thin pore-containing layer. Where high fluxis achieved using larger, less selective micropores in the microporousbarrier, adequate separation may be achieved. Often the pores for thesetypes of membranes have an average pore diameter of greater than 5.0 Å(average of length and width), say, 5.0 to 7.0 or 8 Å. Preferably, thestructures have an aspect ratio (length to width) of less than 1.25:1,e.g., 1.2:1 to 1:1. For molecular sieve-containing membranes, exemplarystructures are USY, ZSM-12, SSZ-35, SSZ-44, VPI-8, and Cancrinite. Insome instances, a permeating molecule in a micropore may assist inenhancing selectivity. For instance, a normal hydrocarbon in a pore maydecrease the rate at which a branched hydrocarbon can enter the pore ascompared to another normal hydrocarbon.

High flux can also be achieved using very thin microporous barrier ineither a continuous or discontinuous membrane. The microporous barriercan, if desired, be selected from sieving structures having microporesthat are substantially impermeable to the moiety sought to be retainedon the retentate side. In general, the pores for these types ofmembranes have an average pore diameter of up to 5.5 Å, for instance,4.5 to 5.4 Å. The aspect ratio of the pores of these membranes may varywidely, and is usually in the range of 1.5:1 to 1:1. For molecularsieve-containing membranes, exemplary structures are ZSM-5, silicalite,ALPO-11, ALPO-31, ferrierite, ZSM-11, ZSM-57, ZSM-23, MCM-22, NU-87,UZM-9, and CaA.

Membranes comprising a discontinuous assembly of microporous barrier arecharacterized in that the barrier has a major dimension less than 100nanometers, and the microporous barrier is associated with ameso/macroporous structure defining fluid flow pores, wherein barrier ispositioned to hinder fluid flow through the pores of themeso/macroporous structure. A molecular sieve barrier is “associated”with a meso/macroporous structure when it is positioned on or in thestructure whether or not bonded to the structure. Hence, nano-sizedparticles or islands of molecular sieve are used as barriers for themembranes. The discontinuous, microporous barrier is positioned tohinder fluid flow through fluid flow channels defined by themeso/macroporous structure. The barrier may be at least partiallyoccluding the opening of a fluid flow channel of the meso/macroporousstructure and/or within the fluid flow channel. Due to the small size ofthe particles or islands forming the discontinuous assembly ofmicroporous barrier, some selectivity of separation is achievabledespite the discontinuity.

Typically the size and configuration of the molecular sieve particlesand the size and configuration of the meso/macropores in themeso/macroporous structure will be taken into account in selecting thecomponents for the sieving membranes. With more spherical molecularsieve particles, such as silicalite, it is preferred to select ameso/macroporous structure having pores that are close to the sameeffective diameter. In this manner, the molecular sieve particles, ifplaced in, or partially in, the pores of the meso/macroporous structure,will provide minimal void space for by-pass. More flexibility existswith platelets and irregular shaped molecular sieve particles as theycan overlap with little or no void space. In some instances acombination of molecular sieve configurations may be desirable. Forinstance, a spherical molecular sieve may be drawn into the pores of ameso/macroporous structure with smaller, more plate-like molecular sieveparticles being subsequently introduced. The complementary functions arethat the sphere serves as a support for the plate-like particles and theplate-like particles overlap to reduce by-pass. While the molecularsieves will likely be different compositions, and thus have differentmicroporosity size and configuration, the benefit is enhanced separationwithout undue loss of permeance.

Where zeolitic molecular sieves are used, obtaining small particles isimportant to obtaining the high flux in a discontinuous microporousbarrier. For many zeolites, seed particles are available that are lessthan 100 nanometers in major dimension. Most molecular sieves are madeusing organic templates that must be removed to provide access to thecages. Typically this removal is done by calcination. As discussedlater, the calcination may be effected when the template-containingmolecular sieves are positioned in a macropore such that undueagglomeration is avoided simply by limiting the number of particles thatare proximate. Another technique for avoiding agglomeration of thezeolite particles during calcination is to silate the surface of thezeolite, e.g., with an aminoalkyltrialkoxysilane,aminoalkylalkyldialkoxysilane, or aminoalkyldialkylalkoxysilane. Theamount of silation required will depend upon the size of the zeolite andits composition as well as the conditions to be used for calcination. Ingeneral, between 0.1 to 10 millimoles of silane are used per gram ofzeolite.

Various techniques exist for providing the molecular sieve particles onor in the meso/macroporous support in a manner that at least partiallyoccludes the meso- or macropores in the support. The specific techniqueto be used will depend upon the size and configuration of the molecularsieve particles, the size and configuration of the meso/macropores inthe meso/macroporous structure, and the desired placement of themolecular sieve in or on the meso/microporous structure.

Especially where molecular sieve is placed on the surface of ameso/macroporous structure to occlude at least a portion of the openingof the pores, the meso/macroporous structure may be wet with a solution,or suspension, of nano-sized molecular sieve. The concentration ofmolecular sieve in the suspension should be sufficiently low that upondrying, the resulting layer of molecular sieve is not unduly thick.Advantageously at least a slight pressure drop is maintained across themeso/macroporous structure during the coating such that a driving forcewill exist to draw molecular sieve to any pores in the meso/macroporousstructure that have not been occluded. Usually the suspension will be anaqueous suspension, although suspensions in alcohols and otherrelatively inert liquids can be used advantageously, at a concentrationof between 2 and 30, say 5 and 20, mass percent.

Where a pressure differential is used, the pressure differential isgenerally in the range of 10 to 200 kPa. One or more coats of molecularsieve may be used, preferably with drying between coats. Drying isusually at an elevated temperature, e.g., between 30° C. and 150° C.,for 1 to 50 hours. Vacuum may be used to assist drying. Where zeolitesare used as the molecular sieve, calcining, e.g., at a temperature ofbetween 450° C. and 600° C. may, in some instances, assist in securingthe molecular sieve to the meso/macroporous structure. Calcining mayalso serve to agglomerate the molecular sieve particles and thus reducevoids and the size of voids. Calcining, of course, is not essential tothe broad aspects of this invention and is only required where, forexample, template resides in the micropores.

Where the discontinuous assembly of nano-sized molecular sieve islocated outside the pores of the meso/macroporous structure, it may bedesirable to bond at least a portion of the particles to the surface ofthe structure. This can be accomplished in a number of ways. Forinstance, the surface of the structure can be functionalized withhydroxyl groups or other moieties that would be reactive with a zeoliticmolecular sieve. For polymeric molecular sieves, the surface may befunctionalized with moieties that react, such as addition orcondensation, with functional moieties on the polymer. These techniquesare well known in the art for other applications.

Similar preparation techniques can be used where it is desired toincorporate at least a portion of the molecular sieve particles in thepores of the meso/macroporous structure. The molecular sieve particlesshould be of an appropriate size to enter the meso/macropores. Apressure differential may be used to draw barrier particles into thepores or ultrasonication may be used to aid in getting barrier particlesinto the pores of the meso/macroporous support. The depth of themolecular sieve particles in the pores of the meso/macroporous structureshould not be so great as to unduly reduce permeance. Often, any surfacedeposition of molecular sieve is removed by, e.g., washing.

If desired, zeolitic molecular sieves can be grown in situ in the poresof the meso/macroporous structure to provide a discontinuous membrane.The synthesis may provide discrete particles or islands between otherstructure such as the meso/macroporous structure or other particles.

An example of using other particles to make discontinuous membranes ofzeolitic molecular sieves, involves providing silica, which may have aparticle size of between 5 and 20 nanometers, in or on themeso/macroporous structure. The silica, due to the active hydroxyls onthe surface, serves as a nucleating site for a zeolite-forming,precursor solution, and layers of zeolite can be grown on and betweenthe silica particles.

Materials other than silica particles can be used as nucleating sitesincluding other molecular sieves or seed crystals of the same zeolite.The surface of the meso/macroporous structure can be functionalized toprovide a selective location for zeolite growth. Some zeolites have selfnucleating properties and thus may be used in the absence of nucleatingsites. Examples of these zeolites are FAU and MFI. In these situations,it may be desired to maintain the precursor solution under zeoliteforming conditions for a time sufficient that growth of the zeolitestarts prior to contacting the precursor solution with themeso/macroporous structure.

For example, one method to form a barrier layer is to place a zeoliticmolecular sieve precursor liquid on a meso/microporous structure. Theprecursor is permitted to crystallize under hydrothermal crystallizationconditions, after which the membrane is washed and heated to removeresidual organic material. The molecular sieve material residesprimarily in and occludes the pores of the porous substrate.

The molecular sieve may be of any suitable combination of elements toprovide the sought pore structure. Aluminum, silicon, boron, gallium,tin, titanium, germanium, phosphorus and oxygen have been used asbuilding blocks for molecular sieves such as silica-alumina molecularsieves, including zeolites; silicalite; AlPO; SAPO; and boro-silicates.The precursor includes the aforementioned elements, usually as oxides orphosphates, together with water and an organic structuring agent whichis normally a polar organic compound such as tetrapropyl ammoniumhydroxide. Other adjuvants may also be used such as amines, ethers andalcohols. The mass ratio of the polar organic compound to the buildingblock materials is generally in the range of 0.1 to 0.5 and will dependupon the specific building blocks used. In order to prepare thin layersof molecular sieves in the membranes, it is generally preferred that theprecursor solution be water rich. For instance, for silica-aluminamolecular sieves, the more ratio of water to silica should be at least20:1 and for aluminophosphate molecular sieves, the mole ratio should beat least 20 moles of water per mole of aluminum.

The crystallization conditions are often in the range of 80° C. to 250°C. at pressures in the range of 100 to 1000, frequently 200 to 500, kPaabsolute. The time for the crystallization is limited so as not to forman unduly thick layer of molecular sieve. In general, thecrystallization time is less than 50, say, 10 to 40, hours. Preferablythe time is sufficient to form crystals but less than that required toform a molecular sieve layer of 200 nanometers, say, 5 to 50 nanometers.The crystallization may be done in an autoclave. In some instances,microwave heating will effect crystallization in a shorter period oftime. The membrane is then washed with water and then calcined at 350°to 550° C. to remove any organics.

Especially with some zeolitic molecular sieve materials, makingparticles less than 100 nanometers is troublesome. Moreover, even withthe use of seed crystals, the particle size may be larger than desired.Another embodiment in making a discontinuous barrier membrane is tosynthesize the zeolite in open regions between particles (substrateparticles) having a major dimension less than 100 nanometers.Accordingly, the major dimension of the microporous barrier can be lessthan 100 nanometers. The substrate particles serve as a nucleating sitefor the zeolite formation and thus are selected from materials havingcapability of nucleating the growth of the zeolite. Examples of suchmaterials are silica, especially silica having a major dimension ofbetween 5 and 50 nanometers and other zeolites having major dimensionsless than 100 nanometers. The use of fumed silica as the substrateparticle is particularly useful for making an AlPO microporous barrier.

The growth of the zeolite on the substrate particle may occur before orafter the substrate particle is used in forming the membrane composite.

Advantageously, the growth of the zeolite on the substrate particlesoccurs while drawing the synthesis liquor through the composite. Thistechnique helps ensure that the growth occurs not as a layer on top ofthe particles, but in the interstices between the particles. Thepressure drop increases as the zeolite growth occurs, and the pressuredrop can be used as an indicator when adequate zeolite formation hasoccurred.

Polymeric molecular sieves can be synthesized in the meso/macroporousstructure. One method for synthesizing a small polymeric molecular sieveis to functionalize nano-particles and/or the meso/macroporous structurewith a group that can react with an oligomer such as through acondensation or addition reaction. For instance, the functional groupsmay provide a hydroxyl, amino, anhydride, dianhydride, aldehyde, amicacid, carboxyl, amide, nitrile, or olefinic moiety for addition orcondensation reaction with a reactive moiety of an oligomer. Suitableoligomers may have molecular weights of 30,000 to 500,000 or more andmay be reactive oligomers of polysulfones; poly(styrenes) includingstyrene-containing copolymers; cellulosic polymers and copolymers;polyamides; polyimides; polyethers; polyurethanes; polyesters; acrylicand methacrylic polymers and copolymers; polysulfides, polyolefins,especially vinyl polymers and copolymers; polyallyls;poly(benzimidazole); polyphosphazines; polyhydrazides; polycarbodiides,and the like.

The synthesis in situ of the molecular sieve, whether it be inorganic ororganic, can be under suitable conditions. A preferred techniqueinvolves conducting the synthesis while drawing the reactant solution,e.g., the precursor solution or oligomer solution through themeso/macroporous structure. This technique provides the benefit ofdirecting the reactant solution to voids that have not been occluded aswell as limits the extent of growth of the molecular sieve as no freshreactant will be able to enter the reaction site once the molecularsieve has occluded the meso- or macropore.

The molecular sieve on polymer support membranes or polymeric supportsthemselves may also be pyrolyzed in a vacuum furnace to produce a carbonmembrane. For such membranes containing molecular sieves, the porestructure of the carbon support is preferably of sufficient diameter tominimize the resistance to the flow of fluids with the molecular sievestructure doing the separation. The temperature of the pyrolysis willdepend upon the nature of the polymer support and will be below atemperature at which the porosity is unduly reduced. Examples ofpolymeric supports include polyimides, polyacrylonitrile,polycarbonates, polyetherketones, polyethersulfones and polysulfones,and prior to pyrolysis, the supports have pores or openings in the rangeof 2 to 100, preferably 20 to 50, nanometers.

Continuous membranes may be prepared by any suitable technique.Typically, the thickness of the microporous barrier will be related tothe duration of the deposition or growth of the microporous barrier onthe meso/macroporous structure. The microporous barrier may be formed byreducing the pore size of an ultrafiltration membrane (effective porediameters of 1 to 100 nanometers) or a microfiltration membrane(effective pore diameters of 100 to 10,000 nanometers) by, e.g., organicor inorganic coating of the channel either interior of the surface, orpreferably, at least partially proximate to the opening of the channel.The deposited material serves to provide a localized reduction of thepores or openings through the support to a size which permits thedesired sieving without unduly reducing the diameter of the remainingpore structure in the support. Examples of vapor depositable materialsinclude silanes, paraxylylene, alkylene imines, and alkylene oxides.Another technique for reducing pore size is to deposit a coke layer onthe meso/macroporous structure. For instance, a carbonizable gas such asmethane, ethane, ethylene or acetylene can be contacted with thestructure at sufficiently elevated temperature to cause coking. Thepreferred porous supports are ultrafiltration membranes having poresizes of between 1 and 80, preferably between 2 and 50, nanometers.

For zeolitic, continuous membranes, one fabricating technique involvescontacting the surface of the meso/macroporous structure with precursorfor molecular sieve and growing the molecular sieve for a timesufficient to achieve the sough film thickness. The procedures disclosedabove can be used to synthesize the molecular sieve. In some instances,it may be desirable to occlude, e.g., with a wax, the meso/macropores ofthe support to prevent undue growth of zeolite in those pores. The waxcan subsequently be removed.

Various techniques are available to enhance the selectivity of high fluxmembranes. Numerous techniques exist to cure defects in continuous ordiscontinuous membranes. As the membranes need not exhibit high C₆Permeate Flow Ratios to be useful for many applications, any techniquethat increases resistance to flow through the defects will serve toimprove membrane performance. For instance, a silica sol overlay coatingmay be used to occlude interstitial openings between the molecular sievecrystals or remaining large pores in the support regardless of how themembrane is prepared.

Another technique to occlude large pores is to provide on one side ofthe barrier layer a large, reactive molecule which is not able topermeate the micropores of the barrier and on the other side a crosslinking agent. The major defects, and to some extent the minor defectsbecome filled with the large, reactive molecule and are fixed bycrosslinking. The unreacted large molecule component can then be removedas well as unreacted crosslinking agent. The large molecule may be anoligomer or large molecule.

For discontinuous membranes, solid may be provided in at least a portionof the voids between particles or islands of microporous barrier andbetween the microporous barrier and the meso/microporous structure.

One generic technique for enhancing the selectivity of a sievingmembrane is to agglomerate adjacent particles of molecular sieve toreduce or substantially eliminate voids between the particles andbetween the particles and walls of the pore structure in themeso/macroporous structure. Because the particles are nano-sized and thenumber of adjacent particles can be relatively few, the agglomerationcan occur while still retaining desirable Permeant Flow Rates. Forpolymeric molecular sieves that are thermoplastic, the agglomeration canoccur by heating to a temperature where agglomeration occurs but no sohigh as to lose either its microporous structure or its ability toprovide the desired occlusion of the meso- or macropore of themeso/macroporous structure. Agglomeration can also be accomplished bycalcining zeolitic molecular sieves. Calcining tends to agglomeratesmall zeolite particles, especially particles that are neither silatednor otherwise treated to reduce the tendency to agglomerate. Thetemperature and duration of the calcining will depend upon the nature ofthe zeolitic molecular sieve. Usually temperatures of between 450° C.and 650° C. are employed over a period of between 2 and 20 hours.

The agglomeration technique may be used with respect to molecular sieveparticles that are on the surface of the meso/macroporous structure aswell as those within the pores of the structure. Most preferably,agglomeration is used when the molecular sieve particles are locatedwithin the meso- or macropores of the meso/macroporous structure suchthat the major dimension of the agglomerate is less than 200, preferablyless than 100, nanometers. The agglomeration may be effected with orwithout a pressure differential across the membrane. Preferably apressure differential is used to assist in reducing voids through whichfluid can by-pass the molecular sieve.

Another generic technique where the discontinuous assembly of barrierdefines voids is to at least partially occlude at least a portion of thevoids by a solid material therein. Preferably the solid material is apolymer or inorganic material. The solid material may simply reside inthe void or it may adhere or be bonded to the molecular sieve ormeso/macroporous structure. The solid material may be a particle oroligomer that may be preformed and then introduced into the voids or itmay be formed in situ.

In one aspect, the solid material provides a “mortar” with themicroporous barrier particles. The mortar is typically a suitablepolymeric material that can withstand the conditions of the separation.Representative polymers include polysulfones; poly(styrenes) includingstyrene-containing copolymers; cellulosic polymers and copolymers;polyamides; polyimides; polyethers; polyurethanes; polyesters; acrylicand methacrylic polymers and copolymers; polysulfides, polyolefins,especially vinyl polymers and copolymers; polyallyls;poly(benzimidazole); polyphosphazines; polyhydrazides; polycarbodiides,and the like. Preferred polymers are those having porosity such as PIMs(see WO 2005/012397) and polymers in which porosity has been induced bypore forming agents. These polymers have pores that may be 0.3 or more,preferably at least 1, nanometer in major dimension and hence allow forfluid flow to and from the barrier particles.

It is not necessary that all particles be encased in the mortar. Oftenthe average thickness of the mortar layer is less than 100 nanometers,and is preferably no more than the major dimension of the particles. Iftoo much mortar is used, a mixed membrane structure may result, and fluxunduly penalized. Hence, the mass ratio of barrier particles to mortaroften is in the range of between 1:2 to 100:1, preferably between 3:1 to30:1.

The mortar and particles may be admixed, e.g., in a slurry, and thenplaced in association with the microporous structure, or may be providedafter deposition of the particles. The polymer may be formed in situ atthe region containing the barrier particles. The barrier particle may beinert to the polymerization or may have active sites to anchor apolymer. For instance, the particle may be functionalized with areactive group that can bind with the polymer or with monomer undergoingpolymerization, say, through a condensation or addition mechanism suchas discussed above.

A concern is that the mortar occludes the micropores of the molecularsieve. With highly porous polymer such as the PIMs, the effect of anyocclusion can be attenuated. Often, the amount of polymer used for themortar and its molecular weight and configuration is such thatinsufficient polymer is present for encapsulating all the molecularsieve particles.

Frequently, the mass ratio of polymer to molecular sieve is between0.01:1 and 0.3:1. The weight average molecular weight of the polymer issometimes in the range of 20,000 to 500,000, preferably, between 30,000and 300,000.

The mortar may be other than polymeric. For example, where the molecularsieve is a zeolite, a silicon tetraalkoxide can react with the zeoliteand can through hydrolysis form a silica framework or mass between themolecular sieve particles. Usually a dilute aqueous solution of silicontetraalkoxide is used, e.g., containing between 0.5 and 25 mass percentsilicon tetraalkoxide, to assure distribution. The functionalization ofthe zeolite with silicon tetraalkoxide also is useful as a cross-linkingsite with organic polymer, especially those containing functional groupssuch as hydroxyl, amino, anhydride, dianhydride, aldehyde or amic acidgroups that can form covalent bonds with organosilicon alkoxide. Also,the same or different zeolite may be grown between the zeolite particlesand the zeolite particles and the meso/macroporous structure using thetechniques described above.

Yet another approach to reducing bypass is to use two or more sizedparticles in forming the barrier-containing layer. If, for example, themicroporous barrier particles are generally spherical with a nominalmajor dimension of 60 nanometers, the regions between the particles canbe sizable and enable bypass. Incorporating configurationally compatibleparticles in these regions can hinder fluid flow and thus result in agreater portion of the fluid being directed to the barrier particles forthe selective separation. The configuration of the barrier particleswill depend upon the type of barrier particle used. A microporouszeolitic molecular sieve particle having a major dimension of less than100 nanometers will likely have a defined configuration due to itscrystalline structure. Some zeolites tend to have a platelet-typeconfiguration whereas others, such as AlPO-14, have a rod-likestructure. Similarly, polymeric, ceramic, glass and carbon molecularsieve particles may have configurations that are not readily changed.Hence, the configuration of the open regions between particles can varywidely.

Sometimes, the configurationally compatible particles are selected toachieve at least partial occlusion of the region. Thus, for sphericalbarrier particles rod shaped or much smaller configurationallycompatible particles may be desired. The configurationally compatibleparticles may be of any suitable composition given the size andconditions of operation. The particles may be polymeric, includingoligomeric; carbon; and inorganic such as fumed silica, zeolite,alumina, and the like.

DETAILED DESCRIPTION OF THE DRAWING

With reference to the FIGURE, a linear paraffin-containing feedstock issupplied to an isomerization unit via line 102. Hydrogen is provided vialine 104. The combined stream passes to isomerization reactor 106. Theeffluent from isomerization reactor 106 is directed via line 108 tostabilizer column 110. In stabilizer column 110, lights are removed asan overhead via line 112. The lights may be used for any suitablepurpose including for fuel value. The bottoms from stabilizer column 110are passed through line 114 to deisohexanizer 116. An overhead isprovided via line 118 from deisohexanizer 116. A bottoms stream fromdeisohexanizer 116 is removed via line 120. A normal hexane-containingside stream from deisohexanizer 116 is passed via line 122 to theretentate side of membrane separator 124. A stream having a lesserconcentration of linear paraffins is removed from separator 124 via line128. This stream will contain an increased concentration ofmethylcyclopentane. As shown, line 128 directs the retentate fractionfor combination with the overhead in line 118. The permeate fraction isrecycled via line 126 to isomerization reactor 106.

1. An apparatus for isomerization of a feedstock comprising paraffinshaving between 5 and 6 carbon atoms to provide a gasoline fractioncomprising: a. an isomerization reactor (106) being adapted to receivefeedstock at an inlet and having an outlet, b. a deisohexanizer (116)having an inlet in fluid communication with the outlet of isomerizationreactor (106), a lower boiling outlet adapted to remove a lower boilingfraction via line (118), a outlet to provide a side-cut fraction and ahigher boiling outlet; and c. a membrane separator (124) having a feedside inlet in fluid communication with the outlet to provide a side-cutfraction of the deisohexanizer (116), a feed side outlet in direct fluidcommunication with line (118) from the lower boiling outlet of thedeisohexanizer (116), and a permeate outlet in fluid communication withthe inlet of the isomerization reactor (106) wherein the membraneseparator is a sieving membrane having a C₆ Permeate Flow Index of atleast 0.01 and a C₆ Permeate Flow Ratio of at least 1.25:1.
 2. Theapparatus of claim 1 wherein the sieving membrane has an average porediameter of 5.0 to 7.0 Å.
 3. The apparatus of claim 1 wherein thesieving membrane has an average pore diameter of 4.5 to 5.4 Å.
 4. Theapparatus of claim 1 wherein the sieving membrane comprises ZSM-5 orsilicalite.